KR20160013116A - Heat ray-shielding microparticle-containing composition and method for producing same, heat ray-shielding film, and heat ray-shielding laminated transparent base material - Google Patents

Abstract

Provided is a heat ray shielding film exhibiting excellent optical characteristics and high weather resistance using composite tungsten oxide fine particles having polyvinyl acetal resin as a main component and high heat shielding effect. A dispersing agent having an acrylic structure in the main chain and an amino group as a functional group and having a thermal decomposition temperature of 200 ° C or higher and containing a composite tungsten oxide fine particle represented by the general formula M _y WO _Z and having a hexagonal crystal structure, Containing composition having an acrylic structure and having a hydroxyl group or a carboxyl group as a functional group and containing at least one dispersing agent having a thermal decomposition temperature of 200 ° C or higher and a content of an organic solvent having a boiling point of 120 ° C or lower of 5 mass% .

Description

TECHNICAL FIELD [0001] The present invention relates to a heat ray shielding microparticle-containing composition, a heat ray shielding film, and a heat ray shielding laminate transparent base material }

The present invention relates to a composition containing a heat-shielding fine particle and a method for producing the composition, which are applied to the production of a heat-shielding film for use in a laminated transparent substrate having a good visible light transmittance and an excellent heat ray shielding function. Further, the present invention relates to a heat ray shielding film to which the heat ray shielding fine particle-containing composition is applied, and a heat ray shielding laminated transparent substrate using the heat ray shielding film.

As a safety glass used for automobiles and the like, a laminated glass is formed by sandwiching an interlayer film including polyvinyl acetal resin or the like between two sheets of glass. Further, it is also possible to provide the interlayer film with a heat ray shielding function, shield the solar energy incident by the laminated glass,

Layer glass has been proposed.

For example, Patent Document 1 proposes a laminated glass in which a soft resin layer containing a heat-shrinkable metal oxide made of fine tin oxide or indium oxide with a particle diameter of 0.1 占 퐉 or less is present between a pair of plate glasses.

In Patent Document 2, at least two sheets of glass are used in combination of Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, V, and Mo, an oxide, a nitride, a sulfide of the metal, or a dopant of Sb or F to the metal, or an intermediate layer in which these complexes are dispersed.

Patent Document 3 proposes a glass window for automobiles in which a glass component composed of fine particles made of TiO ₂ , ZrO ₂ , SnO ₂ , and In ₂ O ₃ and an organic silicon or organosilicon compound exists between transparent plate members .

In Patent Document 4, an intermediate layer composed of three layers is provided between at least two transparent glass plate bodies, and Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, In , A metal such as Ni, Ag, Cu, Pt, Mn, Ta, W, V and Mo, an oxide, a nitride or a sulfide of the metal or a dopant of Sb or F with respect to the metal, Further, a laminated glass in which the first layer and the third layer of the intermediate layer are resin layers has been proposed.

On the other hand, the Applicant has found that an intermediate layer having a heat ray shielding function is present between two sheet glasses, and the intermediate layer is composed of hexaboride microparticles alone or hexaboride microparticles, ITO microparticles and / or ATO microparticles and a vinyl- Or a heat shielding film containing the fine particles formed on a surface of the intermediate layer located on the inner side of at least one of the plate glass and a heat shielding film containing a vinyl resin present between the two plate glass A laminated glass for heat ray shielding is disclosed as Patent Document 5.

The present applicant also discloses a laminated glass in which an intermediate film is a combination of an ultraviolet ray hardening resin, a composite tungsten compound, and a hexaboride, in Patent Document 6.

Patent Document 1 JPH8-217500 A1 Patent Document 2 JPH8-259279 A1 Patent Document 3 JPH4-160041 A1 Patent Document 4 JPH10-297945 A1 Patent Document 5 JP 2001-89202 A Patent Document 6 JP2010-202495 A

However, as a result of further examination by the present inventors, they found the following problems.

The first problem is that the laminated glass related to the conventional techniques disclosed in Patent Documents 1 to 4 is not sufficiently provided with a heat ray shielding function when a high visible light transmittance is required. Further, the haze value indicating the blurred state of the transparent substrate is required to be 1% or less in the window material for the vehicle and 3% or less in the window material for the building. For example, in the laminated glass for heat ray shielding described in Patent Document 5, There was room for. In addition, the laminated glass for heat ray shielding according to the prior art all exhibited insufficient weather resistance when used for a long time, and showed a decrease (deterioration) in visible light transmittance.

The second problem is that, in addition to optical properties, mechanical properties may be required for laminated glass for heat ray shielding used in various window materials. Specifically, laminated glass such as safety glass requires resistance to penetration. Conventionally, a polyvinyl acetal resin has been used as an intermediate layer in order to impart penetration resistance to the above laminated glass. However, when the composite tungsten oxide fine particles are contained in the polyvinyl acetal resin, the optical characteristics are deteriorated. Therefore, as a second alternative, for example, a heat ray shielding film is disclosed in which a polyvinyl acetal resin is replaced with an ultraviolet ray hardening resin and a composite tungsten compound and a hexavide is contained in an ultraviolet ray hardening resin, as described in Patent Document 6. However, from the viewpoint of satisfying the mechanical strength of the safety glass in the market, polyvinyl acetal resin is required as the resin for the intermediate layer.

The present invention has been made in view of the above problems. A problem to be solved is a heat ray shielding film containing polyvinyl acetal resin as a main component and containing composite tungsten oxide fine particles having a high heat ray shielding effect and exhibiting excellent optical properties and high weather resistance, a method for producing the same, Shielding laminated transparent substrate using the heat-shrinkable fine particle-containing material, and which is excellent in storage stability.

That is, the first invention for solving the above-

The general formula M _y WO _Z (Wherein M is at least one element selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al and Cu; ) And a composition comprising a composite tungsten oxide fine particle having a hexagonal crystal structure and at least two dispersing agents, wherein the dispersant is an amino group having an amino group as a functional group and having a thermal decomposition temperature of not less than 200 ° C At least one polymer dispersant is contained,

Wherein at least one kind of a hydroxyl group polymer dispersant and / or a carboxyl group polymer dispersant having an acrylic structure in its main chain and having a hydroxyl group (-OH group) and / or a carboxyl group (-COOH) as a main chain and having a thermal decomposition temperature of 200 ° C or higher and,

And the content of the organic solvent having a boiling point of 120 占 폚 or less is 5 mass% or less.

In the second invention,

In the first invention,

Wherein the amine value of the amino group polymer dispersant is 5 to 100 mgKOH / g.

According to a third aspect of the present invention,

In the first or second invention,

Wherein the amino group polymer dispersant is contained in an amount of 50 to 9900 parts by weight based on 100 parts by weight of the composite tungsten oxide fine particles.

According to a fourth aspect of the present invention,

In any one of the first to third inventions,

Wherein the organic solvent is at least one selected from the group consisting of toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol and ethanol.

According to a fifth aspect of the present invention,

A heat ray shielding film characterized by comprising the heat ray shielding fine particle containing composition according to any one of the first to fourth aspects, and a polyvinyl acetal resin and a plasticizer kneaded and molded into a film.

According to a sixth aspect of the present invention,

Wherein the heat ray shielding film according to the fifth aspect of the present invention is present between two or more transparent substrates.

According to a seventh aspect of the invention,

The general formula M _y WO _Z (Wherein M is at least one element selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al and Cu; ) And having a hexagonal crystal structure, and a step of dispersing the dispersant in an organic solvent having a boiling point of 120 deg. C or less to obtain a dispersion,

A second step of adding the dispersant or the dispersant dissolved in the organic solvent to the dispersion obtained in the first step and mixing them to obtain a mixture,

And a third step of drying the mixture until the content of the organic solvent contained in the mixture obtained in the second step is 5% by mass or less to obtain a composition containing heat ray shielding fine particles By weight of the heat-shrinkable fine particle-containing composition.

According to an eighth aspect of the invention,

In the seventh invention,

Wherein the composite tungsten oxide fine particles in the dispersion are those having an average particle diameter of 40 nm or less.

The heat ray shielding fine particle-containing composition according to the present invention is added to a polyvinyl acetal resin together with a plasticizer and mixed and kneaded. The composition contains polyvinyl acetal resin as a main component and contains a composite tungsten oxide fine particle having a high heat- A heat ray shielding film exhibiting optical properties and high weather resistance and a heat ray shielding laminated transparent substrate using the heat ray shielding film were obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to a composition containing a heat-shielding fine particle and a method for producing the same, a heat-shielding film using a composition containing a heat-shielding fine particle, and a heat-shielding laminated transparent substrate using the heat-

[1] Composition containing heat ray shielding fine particles

The heat ray shielding fine particle-containing composition according to the present invention contains fine particles having a heat ray shielding function, a dispersant, an organic solvent, and other desired additives.

Hereinafter, each component of the composition containing heat-ray shielding fine particles will be described.

(1) Fine particles having heat ray shielding function

The fine particles having a heat ray shielding function used in the heat ray shielding fine particle-containing composition according to the present invention are composite tungsten oxide fine particles. Since the composite tungsten oxide fine particles largely absorb light in the near infrared region, particularly, a light having a wavelength of 1000 nm or more, the transmission tint is often a blue tint. The particle diameter of the composite tungsten oxide fine particles can be appropriately selected depending on the intended use. For example, when used in an application that maintains transparency, it is preferable that the composite tungsten oxide fine particles have a dispersed particle diameter of 40 nm or less. This is because, if the dispersed particle diameter is less than 40 nm, the light is not completely shielded by scattering, the visibility of the visible light region can be maintained, and transparency can be efficiently maintained at the same time.

Particularly, in the case of applying to the windshield of an automobile with an emphasis on transparency in the visible light region, it is preferable to consider scattering by particles. When the reduction of scattering due to these particles is emphasized, the dispersion particle diameter of the composite tungsten oxide fine particles is preferably 30 nm or less, and more preferably 25 nm or less.

The reason for this is that when the particle size of the dispersed particles is small, scattering of light in a visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. When the light scattering is reduced, when the strong light is irradiated, the heat ray shielding film becomes like a lens glass, and clear transparency can not be obtained. This is because, when the diameter of the dispersed particles is 40 nm or less, the above-mentioned geometric scattering or non-scattering is reduced, and a Rayleigh scattering region is formed. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced with the decrease of the dispersed particle diameter, and the transparency is improved. When the diameter of the dispersed particles is 25 nm or less, the scattered light becomes very small, which is preferable. From the viewpoint of avoiding light scattering, the dispersed particle diameter is preferably small, and if the dispersed particle diameter is 1 nm or more, industrial production is easy.

The amount of the composite tungsten fine particles contained in the heat shielding film is preferably 0.2 g / m2 to 2.5 g / m2 per unit area.

Hereinafter, the composite tungsten oxide fine particles, which are fine particles having a heat ray shielding function, and a method for producing the same will be further described.

(a) Composite tungsten oxide fine particles

As the composite tungsten oxide according to the present invention, a compound represented by the general formula M _y WO _Z (M is at least one element selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al and Cu; 0.1? Y? 0.5; 2.2? Z? 3.0) And a composite tungsten oxide having a hexagonal crystal structure. If the values of y and z are in the ranges of 0.1? Y? 0.5 and 2.2? Z? 3.0 with respect to the composite tungsten oxide, useful heat ray shielding properties can be obtained. The addition amount of the additive element M is preferably 0.1 or more and 0.5 or less, more preferably 0.33. This is because the value calculated theoretically from the hexagonal crystal structure is 0.33, and the preferable optical characteristics can be obtained with the amounts added before and after. In the range of Z, 2.2? Z? 3.0 is preferable. This is because even in the case of a composite tungsten oxide material denoted by M _y WO _Z , a mechanism such as the tungsten oxide material indicated by WO _x described above works, and in the case of z? 3.0, the supply of free electrons by the addition of the above- It is because. Further, from the viewpoint of optical characteristics, it is more preferable that 2.45? Z? 3.00.

Examples of preferable composite tungsten oxide fine particles satisfying the above-mentioned conditions include fine particles of Cs _0.33 WO ₃ , Rb _{0 .33} WO ₃ , K _{0 .33} WO ₃ , and Ba _{0 .33} WO ₃ .

(b) Method for producing composite tungsten oxide fine particles

The composite tungsten oxide fine particles represented by the general formula M _y WO _Z can be obtained by heat-treating the tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere.

First, the tungsten compound starting material will be described. The tungsten compound starting material may be at least one selected from hydrates of tungsten trioxide powder, tungsten dioxide powder or tungsten oxide, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride in an alcohol and drying the tungsten oxide hydrate A tungsten compound powder obtained by dissolving tungsten hexachloride in an alcohol, precipitating by adding water and drying it, or a hydrate powder of tungsten oxide obtained by drying an aqueous solution of tungsten oxide, or a tungsten compound powder obtained by drying an aqueous ammonium tungstate solution, or a metal tungsten powder Or more.

In the case of producing the composite tungsten oxide fine particles, it is more preferable to use an aqueous solution of ammonium tungstate or a solution of tungsten hexachloride from the viewpoint that each element in which the starting material is a solution is easily uniformly mixed. These raw materials can be heat-treated in an inert gas atmosphere or a reducing gas atmosphere to obtain composite tungsten oxide fine particles. Further, a starting material is a tungsten compound containing element M in the form of elemental or compound.

Here, in order to produce a starting material in which each component is uniformly mixed at a molecular level, it is preferable to mix each raw material with a solution, and it is preferable that the tungsten compound starting material containing the element M is soluble in a solvent such as water or an organic solvent Do. For example, tungstate, chloride salt, nitrate salt, sulfate salt, oxalate salt, oxide, carbonate salt, hydroxide and the like containing element M can be exemplified, but not limited thereto, and it is preferable that the solution is in a solution state.

Next, a heat treatment in an inert gas atmosphere or a reducing gas atmosphere will be described. First, the heat treatment conditions in the inert gas atmosphere are preferably 650 DEG C or higher. The starting material heat-treated at 650 ° C or higher has a sufficient near infrared ray absorption power and is efficient as heat ray shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ may be used.

As the heat treatment conditions in the reducing atmosphere, it is preferable that the starting material is first heat-treated at a temperature of 100 ° C or higher and 650 ° C or lower in a reducing gas atmosphere, and then heat-treated at 650 ° C or higher and 1200 ° C or lower in an inert gas atmosphere. The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the composition of the reducing atmosphere includes, for example, Ar, N ₂ Is mixed with H ₂ in an amount of not less than 0.1%, more preferably not less than 0.2%. When H ₂ is 0.1% or more by volume ratio, the reduction can proceed efficiently.

The starting material powder reduced with hydrogen contains a magnetite phase and exhibits good heat ray shielding properties. Therefore, this state can be used as heat ray shielding fine particles.

It is preferable that the surface of the composite tungsten oxide fine particles according to the present invention is surface-treated with a compound containing at least one of Si, Ti, Zr and Al, preferably an oxide, from the viewpoint of improving weatherability. In order to carry out the surface treatment, a known surface treatment may be carried out using a compound organic compound containing at least one of Si, Ti, Zr and Al. For example, the composite tungsten oxide fine particles and the organosilicon compound may be mixed and hydrolyzed.

(2) Dispersing agent

The dispersant used in the heat ray shielding fine particle-containing composition according to the present invention is a dispersant having an amino group as a functional group (sometimes referred to as "amino group polymer dispersant" in the present invention) and a hydroxyl group (-OH group) A polymeric dispersant (sometimes referred to as a " hydroxyl-containing polymer dispersant " in the present invention) is used in combination. Alternatively, an amino group polymer dispersant and a polymer dispersant having a carboxyl group as a functional group (sometimes referred to as "carboxyl group polymer dispersant" in the present invention) are used in combination. Alternatively, the amino group polymer dispersant, the hydroxyl group polymer dispersant, and the carboxyl group polymer dispersant are both used.

The amino group polymer dispersant, the hydroxyl group polymer dispersant, and the carboxyl group polymer dispersant according to the present invention all have an acrylic main chain or an acryl-styrene main chain, and the apparatus for simultaneously measuring the differential thermal and thermal weight (referred to as "TG-DTA" ) Having a thermal decomposition temperature of 200 ° C or higher.

Here, the pyrolysis temperature is a temperature at which the weight reduction due to the initiation of pyrolysis of the dispersant in the TG-DTA measurement is started.

The dispersing agent has a thermal decomposition temperature of 200 ° C or higher. When the polyvinyl acetal resin is kneaded with a heat-ray shielding fine particle-containing composition containing a dispersing agent described later, the dispersing agent is not thermally decomposed. As a result, in the heat ray shielding film or the heat ray shielding laminated transparent substrate according to the present invention, it is possible to avoid the situation in which the inherent optical characteristics such as brown coloration and reduction in visible light transmittance due to thermal decomposition of the dispersant can not be obtained.

Hereinafter, the dispersion of amino group polymer dispersant, hydroxyl group polymer dispersant and carboxyl group polymer according to the present invention will be described in detail.

(a) an amino group polymer dispersant

The amino group polymer dispersant according to the present invention is adsorbed on the surface of the above-mentioned composite tungsten oxide fine particles to prevent aggregation of the above-mentioned composite tungsten oxide fine particles and exert the effect of uniformly dispersing these fine particles in the heat ray shielding film. The amine value of the amino group polymer dispersant is preferably 5 to 100 mgKOH / g, and the molecular weight Mw is preferably 2,000 to 200,000.

The amino group-containing polymer dispersant according to the present invention is a compound having an alkaline group such as an amino group in the molecule of the dispersant. Examples of the compound having an alkaline group such as an amino group in the molecule of such a dispersant include a polyolefin resin having an amino group as an alkaline group, a polyester resin, an acrylic resin, a polyurethane resin and an amide resin.

Preferred examples of commercially available amino group polymer dispersants include Disperbyk-112, Disperbyk-116, Disperbyk-130, Disperbyk-161, Disperbyk-162, Disperbyk-164, Disperbyk-166, Disperbyk-167, Amino polymer dispersants manufactured by Big Chem Japan Co., Ltd., such as Disperbyk-2020, Disperbyk-2020, Disperbyk-2070 and Disperbyk-2150, Amino groups manufactured by Ajinomoto Fine Technos such as Ajisper PB821, Ajisper PB822 and Ajisper PB711 EFKA-4401, EFKA-5044, EFKA-5207, EFKA-6225 and EFKA-6225 manufactured by Kusumoto Chemical Industries, Ltd., such as Disperon DA703-50 and Disperon DA7400, 4330, EFKA-4047, EFKA-4060 and the like, and amino group polymer dispersants manufactured by BASF Japan.

The content of the amino group polymer dispersant in the heat ray shielding fine particle-containing composition according to the present invention is preferably 50 parts by weight or more and 9900 parts by weight or less, more preferably 50 parts by weight or more and 1,000 parts by weight or more per 100 parts by weight of the composite tungsten oxide fine particles By weight or less, more preferably 50 parts by weight or more and 500 parts by weight or less. This is because when the content of the amino group polymer dispersant is in the above range, the composite tungsten oxide fine particles are uniformly dispersed in the heat shielding film and the transparency of the heat shielding film is improved. Concretely, the haze value of the heat shielding film can be reduced by incorporating at least 50 parts by weight of the amino group polymer dispersant into 100 parts by weight of the composite tungsten oxide fine particles, and it is contained in an amount of 9,900 parts by weight or less. And the penetration resistance of the intermediate layer constituted by the heat ray shielding film in the heat ray shielding laminated transparent substrate can be ensured.

The detailed reason why the composite tungsten oxide can be dispersed in the polyvinyl acetal resin by adding an appropriate amount of the amino group-containing polymer dispersant according to the present invention to the heat ray shielding fine particle-containing composition of the present invention is unknown. The present inventors believe that the amino group of the amino group polymer dispersant acts on the surface of the composite tungsten oxide fine particles and also attracts the polyvinylacetal resin molecule to each other by an intermolecular force so that the composite tungsten oxide fine particles can be dispersed . And if the dispersion of the fine particles of the composite tungsten oxide is good, the haze value of the heat shielding film is lowered as a result.

(b) a hydroxyl group polymer dispersant, a carboxyl group polymer dispersant

The hydroxyl group polymer dispersant according to the present invention and the carboxyl group polymer dispersant according to the present invention are all adsorbed on the surfaces of the above-mentioned composite tungsten oxide fine particles to prevent aggregation of the composite tungsten oxide fine particles and uniformly disperse these fine particles in the heat ray shielding film It is possible to improve the heat resistance of the resin containing the composite tungsten oxide fine particles and the amino group polymer dispersant according to the effect of dispersing and to thereby exhibit the effect of preventing yellowing deterioration due to heat.

The OH value of the hydroxyl group-containing polymer dispersant according to the present invention is preferably 10 to 200 mgKOH / g, and the molecular weight Mw is preferably 1000 to 150000. Examples of the hydroxyl group polymer dispersant related to the present invention include an acrylic resin having a hydroxyl group (which may be referred to as an acryl polyol) and an acryl-styrene copolymer having a hydroxyl group. Examples of the hydroxyl group-containing polymer dispersing agent include commercially available products such as acrylic polyol and UH series manufactured by Toagosei Co., Ltd.

The acid value of the carboxyl group-containing polymer dispersant according to the present invention is preferably 0.1 to 100 mgKOH / g, and the molecular weight Mw is preferably 2000 to 200000.

Examples of the carboxyl-based polymer dispersant related to the present invention include acrylic resins having a carboxyl group and acrylic styrene copolymers.

Examples of the carboxyl-based polymer dispersing agent include resins manufactured by Mitsubishi Rayon Co., Ltd., such as a commercially available DIANAL BR series, resins manufactured by Toagosei Co., Ltd., such as UC series and UF series.

The content of the hydroxyl group polymer dispersant and / or the carboxyl group polymer dispersant in the heat ray shielding fine particle-containing composition of the present invention is preferably in the range of 5 parts by weight or more and 1,000 parts by weight or less based on 100 parts by weight of the composite tungsten oxide fine particles, More preferably 20 parts by weight or more and 400 parts by weight or less. This is because the content of the hydroxyl group polymer dispersant and / or the carboxyl group polymer dispersant is in the above range, and the heat ray shielding film of the present invention containing the composite tungsten oxide fine particles and the amino group polymer dispersant can be improved in heat resistance, It is possible to maintain the optical characteristics and the mechanical characteristics of the light emitting diode well. Further, by the knitting of the above-mentioned dispersant, long-term preservability of the heat ray shielding fine particle-containing composition according to the present invention can be ensured.

(3) Organic solvents

The organic solvent used in the heat ray shielding fine particle-containing composition according to the present invention preferably has a boiling point of 120 캜 or lower. If the boiling point of the organic solvent is 120 캜 or less, it is easy to dry and remove the organic solvent by drying under reduced pressure. As a result, the removal of the organic solvent by the step of reduced pressure drying proceeds rapidly, contributing to the productivity of the composition containing the heat-shielding fine particles. Further, since the step of reduced-pressure drying is easy and sufficiently progressed, it is possible to avoid the excess organic solvent remaining in the heat ray shielding fine particle-containing composition of the present invention. As a result, occurrence of inconveniences such as generation of bubbles at the time of molding the heat shielding film can be avoided. Specific examples thereof include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol and ethanol. If the fine particles capable of exhibiting a heat ray shielding function at a boiling point of 120 ° C or lower can be uniformly dispersed, . The compounding amount of the organic solvent with respect to the fine particles having a heat ray shielding function will be described in the section (1) of the method for producing a composition containing heat ray shielding fine particles described later.

(4) Other additives

The heat ray shielding fine particle-containing composition according to the present invention can also be blended with common additives. For example, dyes and pigments generally used for coloring thermoplastic resins, such as azo dyes, cyanine dyes, quinoline dyes, perylene dyes, and carbon black, for imparting an arbitrary hue as required, Maybe. Organic ultraviolet absorbers such as a hindered phenol antioxidant, phosphorus antioxidants, release agents, hydroxybenzophenone antioxidants, salicylic antioxidants, HALS antioxidants, triazole antioxidants and triazine antioxidants; inorganic ultraviolet absorbers such as zinc oxide, titanium oxide, , A coupling agent, a surfactant, and an antistatic agent may be added as additives.

[2] Method for producing composition containing heat ray shielding fine particles

The heat ray shielding fine particle-containing composition according to the present invention is a composition comprising a first step of dispersing fine particles having a heat ray shielding function and a dispersant in an organic solvent to obtain a dispersion liquid, a dispersing agent dissolved in a dispersant or an organic solvent And a third step of drying the mixture obtained by the second step and the second step of mixing to remove the organic solvent until the residual amount of the organic solvent becomes not more than 5 mass% do. Hereinafter, each manufacturing process relating to the method for producing the heat-ray shielding fine particle-containing composition will be described.

(1) a step of dispersing fine particles having a heat ray shielding function and a dispersant in an organic solvent to obtain a dispersion (first step)

 The method of dispersing the composite tungsten oxide fine particles into the organic solvent may be arbitrarily selected as long as the fine particles are uniformly dispersed in the organic solvent. For example, a method such as a bead mill, a ball mill, a sand mill, and ultrasonic dispersion may be used.

The concentration of the composite tungsten oxide fine particles in the organic solvent is preferably 5 to 50 mass%. If the amount is 5% by mass or more, it is possible to avoid a situation in which the amount of the organic solvent to be removed becomes too large to increase the production cost. If the content is 50% by mass or less, aggregation of the fine particles tends to occur easily, thereby making it difficult to disperse the fine particles, and it is possible to avoid the situation that the viscosity of the liquid remarkably increases and the handling becomes difficult.

The composite tungsten oxide fine particles in the dispersion are preferably dispersed in an average particle diameter of 40 nm or less. If the average particle diameter is 40 nm or less, optical properties such as haze of the heat ray shielding film after processing can be more preferably improved.

It is also conceivable to disperse the composite tungsten oxide fine particles in a plasticizer to be added to the dispersing agent and the heat ray shielding film to be described later. However, if the composite tungsten oxide fine particles and the dispersing agent are dispersed in the plasticizer, the plasticizer may have a viscosity higher than that of the organic solvent, so that it takes a long time to disperse. Therefore, it is preferable to employ the first step and the second and third steps described below as the production step of the composition for heat ray shielding fine particles according to the present invention.

(2) a step of adding a dispersant or a dispersant dissolved in the above-mentioned organic solvent to the dispersion obtained through the first step to obtain a mixture (second step)

The amino group polymer dispersant, the hydroxyl group polymer dispersant, and / or the carboxyl group polymer dispersant, which have been previously dissolved in the electric organic solvent or directly, are dispersed in the dispersion obtained in the first step, A polymer dispersant is mixed to obtain a mixture. As the mixing method, a known mixing method may be used.

(3) a step of drying the mixture obtained through the second step and removing the organic solvent until the residual amount of the organic solvent after drying becomes 5% by mass or less (third step)

The third step is a step performed to remove the organic solvent in the mixture obtained through the second step and to obtain the heat ray shielding fine particle-containing composition of the present invention. The second step is preferably carried out by drying the resulting mixture under reduced pressure. Specifically, the mixture is dried under reduced pressure with stirring to separate the composition containing the heat-shielding fine particles and the organic solvent component. As a device for use under reduced pressure drying, a vacuum stirring type drier can be mentioned, but it is not particularly limited as long as it is a device having the above functions. In addition, the pressure value at the time of decompression in the drying step is appropriately selected.

By using the above reduced-pressure drying method, the removal efficiency of the solvent is improved, and since the mixture is not exposed to high temperature for a long time, aggregation of the fine particles dispersed in the mixture does not occur, which is preferable. In addition, the productivity also rises, and it is also easy to recover the evaporated organic solvent, and it is also preferable from the environmental consideration.

It is required that the residual organic solvent in the heat-shrinkable fine particle-containing composition obtained after the drying step is 5 mass% or less. When the remaining amount of the organic solvent is 5% by mass or less, bubbles are not generated when the heat ray shielding fine particle-containing composition is processed on the heat-shunting laminated transparent base material, and the appearance and optical characteristics are maintained satisfactorily.

[3] A heat ray shielding film using a composition containing a heat ray shielding fine particle

The heat ray shielding film according to the present invention can be obtained by mixing and kneading the aforementioned heat ray shielding fine particle-containing composition, the polyvinyl acetal resin, the plasticizer and other additives or the adhesive strength adjusting agent as desired, and then kneading them by a known method such as an extrusion molding method, For example, into a film shape.

Hereinafter, characteristics of a polyvinyl acetal resin, a plasticizer, an adhesive power adjuster, a method of manufacturing a heat shielding film, and a heat shielding film will be described.

(1) Polyvinyl acetal resin

As the polyvinyl acetal resin, a polyvinyl butyral resin is particularly preferable.

Further, after consideration of the physical properties of the heat shielding film, a plurality of polyvinyl acetal resins having different degrees of acetalization may be used in combination. Further, a copolyvinyl acetal resin obtained by reacting plural kinds of aldehydes in combination during acetalization can also be used.

The lower limit of the degree of acetylation of the polyvinyl acetal resin is 60%, and the upper limit is more preferably 75%. The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with aldehyde.

The raw material polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and in general, polyvinyl alcohol having a degree of saponification of 80 to 99.8 mol% is used.

The lower limit of the polymerization degree of the polyvinyl alcohol is 200, and the upper limit is preferably 3000. When the degree of polymerization is 200 or more, resistance to penetration of the obtained heat ray shielding laminated transparent substrate is maintained, and safety of the heat ray shielding laminated transparent substrate is maintained. On the other hand, if the degree of polymerization is 3,000 or less, the moldability of the resin film is good, and the rigidity of the resin film is not too large, and the processability is maintained.

The aldehyde is not particularly limited and an aldehyde having 1 to 10 carbon atoms such as n-butylaldehyde, isobutylaldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, n-octylaldehyde and acetaldehyde is generally used . Among them, n-butylaldehyde, n-hexylaldehyde and n-valeraldehyde are preferable, and butylaldehyde having 4 carbon atoms is more preferable.

(2) a plasticizer

The plasticizer used in the heat-shrinkable film and the heat-shrinkable laminated transparent substrate according to the present invention may be a plasticizer such as an ester plasticizer such as a monohydric alcohol and an organic acid ester compound or a polyhydric alcohol organic acid ester compound or an organic phosphoric acid plasticizer And it is preferable that all of them are liquid at room temperature. Especially, an ester compound synthesized from a polyhydric alcohol and a fatty acid is more preferable.

The ester compound synthesized from a polyhydric alcohol and a fatty acid is not particularly limited, and examples thereof include glycols such as triethylene glycol, tetraethylene glycol and tripropylene glycol, and esters of polyhydric alcohols such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, a glycol ester compound or tetraethylene glycol, tripropylene glycol, and an organic acid obtained by a reaction with an alkaline organic acid such as n-octyl acid, 2-ethylhexyl acid, pelaric acid (n-nonyl acid) , And the like. Among them, fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutylate, triethylene glycol dioctanoate and triethylene glycol di-2-ethylhexanoate are very suitable . The choice of the plasticizer is preferably triethylene glycol di-2-ethylhexanate, triethylene glycol di-2-ethylbutylate and tetraethylene glycol di-2-ethylhexanate with care for hydrolysis.

As described above, the fatty acid esters of triethylene glycol are excellent in processability and economical efficiency because they have various properties such as compatibility with polyvinyl acetal and cold resistance in a balanced manner.

Further, another plasticizer may be further added in consideration of the physical properties of the heat shielding film. For example, an ester compound of a polyalcoholic carboxylic acid such as adipic acid, sebacic acid, or azelaic acid and an alcohol having a straight-chain or branched structure having 4 to 8 carbon atoms or a phosphate-based plasticizer may be added.

The total amount of these plasticizers added to the heat shielding film can be determined by considering the physical properties of the heat shielding film. The total added amount is preferably 10% by mass to 70% by mass.

(3) Adhesion modifier

It is also preferable to add an adhesive force adjusting agent to the heat ray shielding film of the present invention. As the adhesive force adjusting agent, an alkali metal salt and / or an alkaline earth metal salt are suitably used. Examples of the acid of the counterpart constituting the salt include carboxylic acids such as octylic acid, hexylic acid, butyric acid, acetic acid and formic acid, and inorganic acids such as hydrochloric acid and nitric acid.

Among the alkali metal salts and / or alkaline earth metal salts, a carboxylic acid magnesium salt having 2 to 16 carbon atoms and a potassium carboxylate salt having 2 to 16 carbon atoms are more preferred.

Examples of the carboxylic acid magnesium salt or potassium salt of the organic acid having 2 to 16 carbon atoms include, but not limited to, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, Potassium carbonate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are most suitably used. These may be used alone, or two or more of them may be used in combination.

Further, if it is a sodium carboxylate salt of potassium, magnesium, calcium or cerium, it can combine an action as an adhesive force adjusting agent and an action of improving the durability of the composite tungsten oxide fine particles.

(4) Manufacturing method of heat shielding film

The heat ray shielding film according to the present invention can be obtained by mixing and kneading a composition containing a heat ray shielding fine particle as described above with a polyvinyl acetal resin and a plasticizer and then molding them into a film form by a known method such as an extrusion molding method or a calendar molding method .

The thickness of the heat ray shielding film according to the present invention is preferably 300 탆 or more and 2,000 탆 or less. When the film thickness of the heat ray shielding film is 300 m or more, it is possible to obtain the intrinsic viscosity required for the heat ray shielding laminated transparent substrate using the heat ray shielding film. If the thickness of the heat ray shielding film is 2.000 탆 or less, the thickness of the transparent base material does not exceed the thickness of the heat ray shielding laminated transparent substrate using the heat ray shielding film. From these viewpoints, it is more preferable that the film thickness of the heat ray shielding film according to the present invention is 400 m or more and 1,200 m or less.

(5) Characteristics of heat shielding film

In the heat ray shielding laminated transparent substrate in which the heat ray shielding film according to the present invention is sandwiched between a pair of inorganic glass, the haze value is not more than 2.0%, the visible ray transmittance is not less than 70%, and the solar radiation transmittance in the wavelength range of 300 to 2,100 nm, Had a heat ray shielding property of 60% or less of visible light transmittance. Also, even when the above heat ray shielding laminated transparent substrate was left in the atmosphere at 120 캜 for 5 days, the change in the yellowish value was within 10 by the change amount b * of b *.

When the haze value exceeds 2.0%, the transparency of the interlayer film or the laminated transparent substrate is remarkably impaired, and when the change of? B * exceeds 10, the change can be visually confirmed. Considering that the heat ray shielding film according to the present invention It has been found that there are sufficient optical properties and durability.

[4] heat shielding laminated transparent substrate using heat shielding film

The heat ray shielding laminated transparent substrate according to the present invention is obtained by adhering a transparent substrate such as two sheets of inorganic glass having a heat shielding film thereon by a known method and integrating them. The heat ray shielding laminated glass thus obtained can be used mainly as windshields for automobiles or windows for buildings.

A heat shielding film is sandwiched between opposed transparent substrates using a transparent resin instead of the inorganic glass as the transparent substrate, or a heat shielding film is sandwiched between the opposed transparent substrates by using the transparent resin and the inorganic glass in combination Thereby obtaining a heat ray shielding laminated transparent substrate. Applications are the same as heat-ray shielding laminated glass.

It is of course possible to use a heat ray shielding film as a single unit or a transparent substrate such as an inorganic glass or a transparent resin in the presence of a heat ray shielding film on one side or both sides. As the inorganic glass, high heat ray absorbing glass, clear glass, green glass and the like are used. The high heat ray absorbing glass refers to a heat ray absorbing glass having a visible light transmittance of 75% or more and a transmittance of 65% or less in the entire wavelength range of 900 to 1300 nm.

[5] Theorem

As described in detail above, a dispersion obtained by dispersing at least one of the composite tungsten oxide fine particles, the amino group polymer dispersant, the hydroxyl group polymer dispersant, or the carboxyl group polymer dispersant in an organic solvent having a boiling point of 120 캜 or less as a heat ray shielding component , The organic solvent was removed up to 5 mass% or less by using the reduced pressure drying method to obtain a composition containing heat ray shielding fine particles. By mixing the heat ray shielding fine particle-containing composition, the polyvinyl acetal resin, and the plasticizer and kneading them into a film shape by a known method, the maximum transmittance in the visible light region and the strong absorption in the near infrared region It becomes possible to manufacture a heat ray shielding film for a heat ray shielding laminated transparent material. Further, the heat ray shielding laminated transparent substrate according to the present invention uses a polyvinyl acetal resin as the resin for the intermediate layer, and satisfies the mechanical strength of the safety glass.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

The visible light transmittance and solar radiation transmittance of the heat-shrinkable laminated transparent substrate in each of Examples and the color taste (10 ° field of view, light source D65) of the film were measured using a spectrophotometer U-4000 manufactured by Hitachi Seisakusho Co., Respectively. The solar radiation transmittance is an index showing the heat ray shielding performance of the heat ray shielding laminated transparent substrate.

The haze value was measured based on JIS K 7105 using HR-200 manufactured by Murakami Color Research Laboratory Co., Ltd.

[Example 1]

Composite tungsten oxide fine particles Cs _{0 .33} WO ₃ (Hereinafter referred to as fine particles (a)) 10% by mass, an amino group polymer dispersant (dispersant having an acrylic main chain, an amino group as a functional group, an amine value of 40 mgKOH / g and a thermal decomposition temperature of 230 deg. (Hereinafter abbreviated as (A)) and 86 mass% of methyl isobutyl ketone (MIBK). These were pulverized and dispersed in a paint shaker with 0.3 mm? ZrO ₂ beads for 7 hours to prepare a composite tungsten oxide fine particle dispersion (hereinafter abbreviated as (A) liquid).

Here, the dispersion mean particle diameter of the fine particles (a) in Solution A was 22 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso.

(A) having a molecular weight Mw of 14,000, an acid value of 90 mgKOH / g, a thermal decomposition temperature (Tg), and a hydroxyl group-containing polymer dispersant (A) and the dispersing agent (B) so that the weight ratio of the dispersing agent (A): dispersing agent (A): dispersing agent (B) is 1: 1: Were added, and they were loaded in a stirring type vacuum dryer. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (A)) of Example 1. As a result, 100 parts by weight of the dispersant (A) as the amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a).

The methyl isobutyl ketone content in the obtained composition (A) was 2.7% by mass.

0.6% by mass of the obtained composition (A), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition and the mixture was loaded in a twin-screw extruder . The resin composition was kneaded at 200 占 폚 and extruded from a T-die to give a heat-shrinkable film for a hot-wire laminating transparent material (hereinafter abbreviated as shielding film (A)) according to Example 1 in a thickness of 0.7 mm by calender roll method.

The resulting shielding film (A) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (A1)) of Example 1 was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (A1) had a solar radiation transmittance of 44.7% and a haze value of 0.9% when the visible light transmittance was 77.9%.

On the other hand, the shielding film (A) was placed in a thermostatic bath at 120 占 폚 and subjected to a heat resistance test for 5 days. Then, the shielding film (A) was put in two inorganic glasses and the heat ray shielding laminated glass Quot;). At this time, the yellow value b * between the laminated transparent base material (A1) and the transparent base material (A2) was measured, and the difference? B * was 4.64. The results are shown in Table 1.

The composition (A) was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (A), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed, Lt; / RTI > The resin composition was kneaded at 200 占 폚 and extruded with a T-die to form a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter, abbreviated as shielding film A ') according to Example 1, ≪ / RTI >

The obtained shielding film (A ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (A3)) according to Example 1 was obtained by a publicly known method.

As shown in Table 1, the optical properties of the laminated transparent base material (A3) had a solar radiation transmittance of 45.2% and a haze value of 0.8% when the visible light transmittance was 78.3%. The results are shown in Table 1.

[Example 2]

(A): dispersing agent (A): dispersing agent (B) = dispersant (B) in the component was obtained by adding a dispersant to the liquid (A) obtained in Example 1, 1: 1: 0.5, and these were loaded in a stirring type vacuum dryer. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (B)) of Example 2. As a result, in the composition (B), 100 parts by weight of the dispersant (A) as the amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The content of methyl isobutyl ketone in the obtained composition (B) was 3.1% by mass.

0.5% by mass of the obtained composition (B), 28.5% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to obtain a resin composition, . Then, the above resin composition was kneaded at 200 占 폚 and extruded from a T-die to give a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as shielding film (B)) according to Example 2 with a thickness of 0.7 mm by calender roll method .

The obtained shielding film (B) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (B1)) of Example 2 was obtained by a known method. As shown in Table 1, the optical characteristics of the laminated transparent base material B1 were 44.9% in the solar transmittance and 1.0% in the haze value when the visible light transmittance was 78.2%.

On the other hand, the shielding film (B) was placed in a thermostatic bath at 120 캜 for 5 days, and then the film was sandwiched between two sheets of inorganic glass. The heat ray shielding laminated glass of Example 2 Quot;). At this time, the yellow value b * in the transparent base material (B2) and the laminated transparent base material B1 together was measured, and the difference? B * was 5.01. The results are shown in Table 1.

The composition (B) was stored at room temperature for 12 months. Then, 0.5% by mass of the stored composition (B), 28.5% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by a calender roll method to obtain a heat ray shielding film for a heat-shunting laminated transparent material (hereinafter abbreviated as a shielding film B ' .

The obtained shielding film (B ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (B3)) of Example 2 was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (B3) had a solar radiation transmittance of 44.5% at a visible light transmittance of 77.8% and a haze value of 1.0%. The results are shown in Table 1.

[Example 3]

(A): Dispersant (A): Dispersant (B) = Dispersing agent (B) The weight ratio of the fine particles (a) 1: 0.5: 2, and these were loaded in a stirring type vacuum dryer. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (C)) of Example 3. As a result, 50 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a) in the composition (C). The content of methyl isobutyl ketone in the obtained composition (C) was 3.9% by mass.

0.7% by mass of the composition (C) obtained, 28.3% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded into a twin screw extruder. Then, the above resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as shielding film (C)) according to Example 3 in a thickness of 0.7 mm by calender roll method .

The obtained shielding film (C) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (C1)) according to Example 3 was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (C1) had a solar radiation transmittance of 45.3% at a visible light transmittance of 78.3% and a haze value of 1.1%.

On the other hand, the shielding film (C) was placed in a thermostatic bath at 120 占 폚 and subjected to a heat resistance test for 5 days. Then, the shielding film was sandwiched between two sheets of inorganic glass, and the heat ray shielding laminated glass Quot;). At this time, the yellow value b * between the laminated transparent base material (C1) and the transparent base material (C2) was measured, and the difference? B * was 3.22. The results are shown in Table 1.

The composition (C) was stored at room temperature for 12 months. Then, 0.7% by mass of the stored composition (C), 28.3% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by calender roll method to obtain a heat ray shielding film for a heat-shunted laminated transparent material for a heat-shunted laminated transparent substrate (hereinafter abbreviated as shielding film C ' .

The obtained shielding film (C ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass according to Example 3 (hereinafter abbreviated as laminated transparent substrate (C3)) was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent substrate (C3) had a solar radiation transmittance of 45.0% and a haze value of 1.1% when the visible light transmittance was 78.0%. The results are shown in Table 1.

[Example 4]

(A), a dispersant (A), a carboxyl group polymer dispersant (having an acrylic main chain, a carboxyl group as a functional group, a molecular weight Mw of 90000, an acid value of 3 mg (A): dispersant (A): dispersant (C) = 1: 1: 1 was used as the dispersant (hereinafter abbreviated as dispersant (C) These were loaded in a stirring type vacuum dryer. The mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (D)) of Example 4. As a result, in Composition D, 100 parts by weight of the dispersing agent (A) as the amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The content of methyl isocetyl ketone in the obtained composition (D) was 2.3% by mass.

0.6% by mass of the obtained composition (D), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer, and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded in a twin-screw extruder. Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shunted laminated transparent material for use in Example 4 (hereinafter abbreviated as shielding film D) .

The obtained shielding film D was sandwiched between two sheets of inorganic glass and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate D1) according to Example 4 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent substrate (D1) were 45.2% at a solar radiation transmittance at a visible light transmittance of 78.0% and a haze value of 1.0%.

On the other hand, the shielding film (D) was placed in a thermostatic bath at 120 캜 for 5 days to be subjected to a heat resistance test, and then sandwiched between two sheets of inorganic glass. The heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate Quot;). At this time, the yellow value b * between the laminated transparent base material (D1) and the transparent base material (D2) was measured, and the difference? B * was 4.50. The results are shown in Table 1.

The composition (D) was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (D), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the above resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as shielding film (D ')) .

The obtained shielding film (D ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (D3)) according to Example 4 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent base material (D3) were 44.7% at a visible light transmittance of 77.9% and a haze value of 1.0% at a visible light transmittance of 77.9%. The results are shown in Table 1.

[Example 5]

(A): Dispersant (A): Dispersant (C) = Dispersing agent (C) The weight ratio of the fine particles (a) 1: 1: 0.5, and these were loaded in a stirring type vacuum dryer. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as Composition E) of Example 5. As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a).

The content of methyl isobutyl ketone in the obtained composition (E) was 3.3% by mass.

0.5% by mass of the composition (E) obtained, 28.5% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition, . Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shunted laminated transparent material (hereinafter abbreviated as shielding film (E) .

The obtained shielding film (E) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass according to Example 5 (hereinafter abbreviated as laminated transparent substrate (E1)) was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (E1) had a solar radiation transmittance of 45.2% and a haze value of 0.8% when the visible light transmittance was 78.3%.

On the other hand, the shielding film (E) was put in a thermostatic bath at 120 캜 for 5 days, then put in two inorganic glasses, and the heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate (E2) Quot;). At this time, the yellow value b * between the laminated transparent base material E1 and the transparent base material E2 was measured, and the difference? B * was 5.20. The results are shown in Table 1.

The composition (E) was stored at room temperature for 12 months. Then, 0.5% by mass of the stored composition (E), 28.5% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition. And loaded. Then, the resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as shielding film (E ')) . The obtained shielding film (E ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (E3)) according to Example 5 was obtained by a known method. As shown in Table 1, the optical properties of the laminated transparent base material (E3) had a solar radiation transmittance of 45.2% and a haze value of 0.8% when the visible light transmittance was 78.3%. The results are shown in Table 1.

[Example 6]

(A): Dispersant (A): Dispersant (C) = Dispersing agent (C) The weight ratio of the fine particles (a) to the dispersing agent 1: 0.5: 2, and these were loaded in a stirring type vacuum dryer. The mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (F)) according to Example 6. As a result, 50 parts by weight of the dispersant (A) as the amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a).

The methyl isobutyl ketone content in the obtained composition (F) was 4.3% by mass.

0.7% by mass of the composition (F) obtained, 28.3% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded in a twin-screw extruder. Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shunted laminated transparent substrate (hereinafter abbreviated as shielding film (F) .

The obtained shielding film F was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate F1) of Example 6 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent base material F1 were 44.8% and the haze value was 0.9% when the visible light transmittance was 77.9%.

On the other hand, the shielding film F was put in a thermostatic bath at 120 캜 for 5 days, then put in two inorganic glasses, and the heat ray shielding laminated glass (hereinafter referred to as the laminated transparent substrate F 2) Quot;). At this time, the yellow value b * between the laminated transparent base material F1 and the transparent base material F2 was measured, and the difference? B * was 3.79. The results are shown in Table 1.

The composition (F) was stored at room temperature for 12 months. Then, 0.7% by mass of the stored composition (F), 28.3% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by calender roll method to obtain a heat ray shielding film for a heat-shunted laminated transparent material for transparent substrate (hereinafter abbreviated as shielding film F ' .

The obtained shielding film (F ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (F3)) according to Example 6 was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (F3) had a solar radiation transmittance of 44.9% and a haze value of 0.9% when the visible light transmittance was 78.1%. The results are shown in Table 1.

[Example 7]

The same procedure was followed as in Example 7 except that the weighing ratios were 10 mass% of the fine particles (a), 4 mass% of the dispersing agent (A), and 86 mass% of toluene, and the dispersion of the composite tungsten oxide fine particles (Hereinafter abbreviated as solution (G)).

The dispersion mean particle diameter of the fine particles (a) in the liquid (G) was 19 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso.

(A): dispersing agent (A): dispersing agent (B) = 1: 1: 1 in the weight ratio of the fine particles (a), the dispersing agent (A) and the dispersing agent (B) (A) and a dispersant (B) were added, and these were loaded in a stirring type vacuum drier. Then, the resultant was dried under reduced pressure at room temperature to remove toluene to obtain a heat-shrinkable fine particle-containing composition (hereinafter, abbreviated as composition (G)) of Example 7. As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The content of toluene in the obtained composition (G) was 2.3% by mass.

0.6% by mass of the obtained composition (A), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition, . Then, the resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as shielding film (G) . The obtained shielding film (G) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (G1)) according to Example 7 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent substrate G1 were 44.8% at a solar radiation transmittance of 78.1% and a haze value of 1.0% at a visible light transmittance of 78.1%.

On the other hand, the shielding film G was put in a thermostatic chamber at 120 캜 for 5 days, and then it was inserted into two inorganic glass pieces. The heat shielding laminated glass of Example 7 (hereinafter, Quot;). At this time, the yellow value b * between the laminated transparent base material (G1) and the transparent base material (G2) was measured, and the difference? B * was 5.01. The results are shown in Table 1.

The composition (G) was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (G), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition. And loaded. Then, the above resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter, abbreviated as shielding film G ' .

The obtained shielding film G 'was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Example 7 (hereinafter abbreviated as laminated transparent substrate G3) was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (G3) had a solar radiation transmittance of 45.1% and a haze value of 0.9% when the visible light transmittance was 78.2%. The results are shown in Table 1.

[Example 8]

The same procedure as in Example 1 was carried out except that the weighing ratios were 10 mass% of the fine particles (a), 4 mass% of the dispersing agent (A), and 86 mass% of methyl ethyl ketone (MEK) (Hereinafter abbreviated as solution (H)) was obtained.

The average particle diameter of the fine particles (a) in the liquid (H) was 25 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso.

(A): dispersing agent (A): dispersing agent (B) = 1: 1: 1 in the weight ratio of the fine particles (a), the dispersing agent (A) and the dispersing agent (B) (A) and a dispersant (B) were added, and these were loaded in a stirring type vacuum drier. Then, the MEK was removed by drying under reduced pressure at room temperature to obtain a heat-shroud fine particle-containing composition (hereinafter abbreviated as composition (H)) of Example 8. As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The MEK content in the obtained composition (H) was 2.3% by mass.

0.6% by mass of the obtained composition (H), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded in a twin-screw extruder. Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shunted laminated transparent material (hereinafter abbreviated as shielding film H) .

The obtained shielding film (H) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (H1)) according to Example 8 was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent base material (H1) had a solar radiation transmittance of 44.7% at a visible light transmittance of 77.9% and a haze value of 0.9%.

On the other hand, the shielding film (H) was placed in a thermostatic bath at 120 ° C for 5 days, then subjected to a heat resistance test for 5 days and then sandwiched between two sheets of inorganic glass. The heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate Quot;). At this time, the yellow value b * between the laminated transparent base material (H1) and the transparent base material (H2) was measured, and the difference? B * was 4.66. The results are shown in Table 1.

Composition (H) was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (H), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition. And loaded. Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by a calender roll method to obtain a heat ray shielding film for a heat-shunted laminated transparent material (hereinafter abbreviated as shielding film H ' .

The obtained shielding film H 'was sandwiched between two sheets of inorganic glass, and the heat ray shielding laminated glass of Example 8 (hereinafter abbreviated as laminated transparent substrate H3) was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent base material (H3) were 45.1% in the solar transmittance and 0.9% in the haze value when the visible light transmittance was 78.3%. The results are shown in Table 1.

[Example 9]

The same procedure as in Example 1 was carried out except that the weight ratio of the fine particles (a) was 10 mass%, the dispersant (A) was 4 mass%, and the content of butyl acetate was 86 mass%, and the composite tungsten oxide fine particles (Hereinafter abbreviated as solution (I)).

Here, the dispersion average particle diameter of the fine particles (a) in the liquid (I) was 31 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso.

(A): dispersing agent (A): dispersing agent (B) = 1: 1: 1 in the weight ratio of the fine particles (a), the dispersing agent (A) and the dispersing agent (B) (A) and a dispersant (B) were added, and these were loaded in a stirring type vacuum drier. Then, vacuum drying was carried out at room temperature to remove butyl acetate, thereby obtaining a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (I)) of Example 9. As a result, 100 parts by weight of the dispersant (A) as the amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The content of butyl acetate in the obtained composition (I) was 4.0% by mass.

0.6% by mass of the obtained composition (I), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition, . Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shunted laminated transparent substrate (hereinafter abbreviated as shielding film (I) .

The obtained shielding film (I) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass according to Example 9 (hereinafter abbreviated as laminated transparent substrate (I1)) was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent base material (I1) were 45.2% at a solar radiation transmittance at a visible light transmittance of 78.3% and a haze value of 1.0%.

On the other hand, the shielding film (I) was placed in a thermostatic chamber at 120 캜 for 5 days, and then the thermostat was put in two inorganic glasses. The heat shielding laminated glass of Example 9 (hereinafter, ) Was obtained. At this time, the yellow value b * between the laminated transparent base material (I1) and the transparent base material (I2) was measured, and the difference? B * was 6.05. The results are shown in Table 1.

Composition (I) was also stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (I), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, And loaded. Then, the above resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shrinkable laminate transparent substrate (hereinafter abbreviated as shielding film (I ')) .

The obtained shielding film I 'was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Example 9 (hereinafter abbreviated as laminated transparent substrate I3) was obtained by a known method. As shown in Table 1, the optical characteristics of the laminated transparent base material (I3) were 45.0% at a solar radiation transmittance at a visible light transmittance of 78.1% and a haze value of 1.0%. The results are shown in Table 1.

[Example 10]

The same procedure as in Example 1 was carried out except that the weight ratio was 10 mass% of the fine particles (a), 4 mass% of the dispersant (A), and 86 mass% of isopropyl alcohol (IPA) Tungsten oxide fine particle dispersion (hereinafter abbreviated as solution (J)).

The dispersion average particle diameter of the fine particles (a) in the liquid (J) was 30 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso.

(A): dispersing agent (A): dispersing agent (B) = 1: 1: 1 in the weight ratio of the fine particles (a), the dispersing agent (A) and the dispersing agent (B) (A) and a dispersant (B) were added, and these were loaded in a stirring type vacuum drier. Then, the IPA was removed by drying under reduced pressure at room temperature to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (J)) of Example 10. As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The IPA content in the obtained composition (J) was 4.0% by mass.

0.6% by mass of the obtained composition (J), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition and then charged in a twin-screw extruder . Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat-shrinkable film for a heat-shunted laminated transparent substrate (hereinafter abbreviated as shielding film J) .

The obtained shielding film (J) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (J1)) of Example 10 was obtained in a known manner. As shown in Table 1, the optical properties of the laminated transparent base material (J1) had a solar radiation transmittance of 45.0% and a haze value of 0.9% when the visible light transmittance was 77.9%.

On the other hand, the shielding film J was put in a thermostatic bath at 120 캜 for 5 days, then put in two inorganic glasses, and the heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate J 2) Quot;). At this time, the yellow value b * between the laminated transparent base material (J1) and the transparent base material (J2) was measured, and the difference? B * was 5.23. The results are shown in Table 1.

Composition (J) was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (J), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition. And loaded. Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as a shielding film J ' .

The obtained shielding film J 'was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate J3) according to Example 10 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent base material J3 were 44.8% at a solar radiation transmittance of 78.0% and a haze value of 1.0% at a visible light transmittance of 78.0%. The results are shown in Table 1.

[Example 11]

The same procedure as in Example 1 was carried out except that the weighing ratios were 10 mass% of the fine particles (a), 4 mass% of the dispersing agent (A), and 86 mass% of ethanol, and the dispersion of the composite tungsten oxide fine particles (Hereinafter referred to as (K) solution).

The dispersion average particle diameter of the fine particles (a) in the liquid (K) was 19 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso.

(A): dispersing agent (A): dispersing agent (B) = 1: 1: 1 in the weight ratio of the fine particles (a), the dispersing agent (A) and the dispersing agent (B) (A) and a dispersant (B) were added, and these were loaded in a stirring type vacuum drier. The resultant was dried under reduced pressure at room temperature to remove ethanol to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (K)) of Example 11. As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The ethanol content in the obtained composition (K) was 1.5% by mass.

0.6% by mass of the obtained composition (K), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, . Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat-shrinkable film for a heat-shunted laminated transparent substrate (hereinafter abbreviated as shielding film K) .

The obtained shielding film K was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate K1) according to Example 11 was obtained in a known manner. As shown in Table 1, the optical properties of the laminated transparent base material (K1) had a solar radiation transmittance of 44.9% and a haze value of 0.9% when the visible light transmittance was 78.0%.

On the other hand, the shielding film K was put in a thermostatic bath at 120 占 폚 and subjected to a heat resistance test for 5 days. Then, the shielding film K was sandwiched between two sheets of inorganic glass and the heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate K2) Quot;). At this time, the yellow value b * between the laminated transparent base material K1 and the transparent base material K2 was measured, and the difference? B * was 4.77. The results are shown in Table 1.

The composition (K) was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (K), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the resin composition was kneaded at 200 占 폚 and extruded from a T-die to form a heat-shrinkable film for a heat-shunted laminated transparent substrate (hereinafter abbreviated as shielding film K ') according to Example 11 so as to have a thickness of 0.7 mm by calender roll .

The obtained shielding film K 'was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate K3) according to Example 11 was obtained in a known manner. As shown in Table 1, the optical characteristics of the laminated transparent base material K3 were 44.9% at a solar radiation transmittance of 78.0% and a haze value of 1.0% at a visible light transmittance of 78.0%. The results are shown in Table 1.

[Example 12]

(A): dispersant (A), dispersant (A), dispersant (B) and dispersant (C) in the component were added to the liquid (A) obtained in Example 1 and the weight ratio of the fine particles Dispersant (B): dispersant (C) = 1: 1: 1: 1, and these were loaded in a stirring type vacuum drier. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (L)) of Example 12. As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a).

The content of methyl isobutyl ketone in the obtained composition (L) was 3.3% by mass.

0.8% by mass of the obtained composition (L), 28.2% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded in a twin-screw extruder. Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by a calender roll method to obtain a heat ray shielding film for a heat ray shielding laminated transparent material for a twelfth embodiment (hereinafter abbreviated as shielding film L) .

The resulting shielding film L was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate L1) of Example 12 was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent substrate (L1) had a solar radiation transmittance of 45.0% at a visible light transmittance of 78.0% and a haze value of 1.0%.

On the other hand, the shielding film L was put in a thermostatic bath at 120 캜 for 5 days and then put in two inorganic glasses, and the heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate L 2) Quot;). At this time, the yellow value b * between the laminated transparent base material (L1) and the transparent base material (L2) was measured, and the difference? B * was 3.99. The results are shown in Table 1.

Composition (L) was also stored at room temperature for 12 months. 0.8% by mass of the thus-stored composition (L), 28.2% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition. And loaded. Then, the resin composition was kneaded at 200 占 폚 and extruded from a T-die to obtain a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as shielding film L ') of Example 12 with a thickness of 0.7 mm by calender roll method . The resulting shielding film L 'was sandwiched between two sheets of inorganic glass, and the heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate L3) of Example 12 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent substrate (L3) were 44.9% in the solar radiation transmittance and 1.0% in haze when the visible light transmittance was 77.9%. The results are shown in Table 1.

[Comparative Example 1]

A dispersant was added to the liquid (A) obtained in Example 1 to adjust the weight ratio of the fine particles (a) and the dispersant (A) in the components to the ratio of the fine particles (a): dispersant (A) = 1: 1, Lt; / RTI > Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition of Comparative Example 1 (hereinafter abbreviated as composition alpha). As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a).

The content of methyl isobutyl ketone in the obtained composition (?) Was 3.0% by mass.

0.4% by mass of the obtained composition (?), 28.6% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded into a twin screw extruder. Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by a calender roll method to obtain a heat ray shielding film for a heat ray shielding laminated transparent material for use in Comparative Example 1 (hereinafter abbreviated as shielding film?) .

The resulting shielding film? Was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass according to Comparative Example 1 (hereinafter abbreviated as laminated transparent substrate? 1) was obtained by a known method. As shown in Table 1, the optical characteristics of the laminated transparent base material (? 1) were 44.7% at a solar radiation transmittance at a visible light transmittance of 78.0% and a haze value of 0.9%.

On the other hand, the shielding film? Was placed in a thermostatic bath at 120 占 폚 for 5 days to be subjected to a heat resistance test, and then put in two inorganic glasses. The heat ray shielding laminated glass of Comparative Example 1 Quot;). At this time, the yellow value b * between the laminated transparent base material (? 1) and the transparent base material (? 2) was measured, and the difference? B * was 25.1. The results are shown in Table 1.

The composition (?) Was stored at room temperature for 12 months. Then, 0.4% by mass of the stored composition (?), 28.6% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > The resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat ray shielding film for a heat-shunted laminated transparent material for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as? .

The resulting shielding film? 'Was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Comparative Example 1 (hereinafter abbreviated as laminated transparent substrate? 3) was obtained by a known method. As shown in Table 1, the optical characteristics of the laminated transparent substrate (? 3) were 44.9% at a solar radiation transmittance of 78.1% and a haze value of 0.9% at a visible light transmittance of 78.1%. The results are shown in Table 1.

[Comparative Example 2]

The same procedure as in Example 1 was repeated except that the weight ratio was 10 mass% of the fine particles (a), 4 mass% of the dispersing agent (B), and 86 mass% of methyl isobutyl ketone (MIBK) (Hereinafter abbreviated as (?) Solution) was obtained.

Here, the dispersion mean particle diameter of the fine particles (a) in the solution (β) was 21 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso Co., Ltd. (B) in the composition was such that the weight ratio of the heat-ray shielding fine particles and the dispersing agent (B) to the heat ray shielding fine particles: dispersing agent (B) was 1: 3, and these were loaded in a stirring type vacuum drier. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (?)) Of Comparative Example 2. As a result, the amino group polymer dispersant was not included in 100 parts by weight of the fine particles (a). The content of methyl isobutyl ketone in the obtained composition (?) Was 3.7% by mass.

0.8% by mass of the obtained composition (?), 28.2% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of a polyvinyl butyral resin were weighed and mixed to prepare a resin composition and loaded in a twin-screw extruder. Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by calender roll method to obtain a heat ray shielding film for a heat ray shielding laminated transparent material for a comparative example 2 (hereinafter abbreviated as shielding film?) .

The obtained shielding film (?) Was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass (hereinafter abbreviated as laminated transparent substrate (? 1)) of Comparative Example 2 was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent substrate (? 1) were 46.2% at a solar radiation transmittance of 77.7% and a haze value of 3.0% at a visible light transmittance of 77.7%.

On the other hand, the shielding film? Was put in a thermostatic bath at 120 占 폚 and subjected to a heat resistance test for 5 days, then put in two inorganic glasses, and heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate? Quot;). At this time, the yellow value b * between the laminated transparent substrate (1) and the transparent substrate (2) was measured, and the difference? B * was 5.97. The results are shown in Table 1.

The composition (?) Was stored at room temperature for 12 months. Then, 0.8% by mass of the stored composition (?), 28.2% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the above resin composition was kneaded at 200 占 폚 and extruded from a T-die to give a heat-shrinkable film for a heat-shrinkable laminated transparent substrate (hereinafter abbreviated as a shielding film? ') .

The obtained shielding film? 'Was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Comparative Example 2 (hereinafter abbreviated as laminated transparent substrate? 3) was obtained by a known method. As shown in Table 1, the optical properties of the laminated transparent substrate (3) had a solar radiation transmittance of 46.7% at a visible light transmittance of 78.0% and a haze value of 2.9%. The results are shown in Table 1.

[Comparative Example 3]

The same procedure as in Example 1 was carried out except that the weight ratio was 10 mass% of the fine particles (a), 3 mass% of the dispersing agent (A) and 87 mass% of methyl isobutyl ketone (MIBK) (Hereinafter abbreviated as (?) Solution) was obtained.

Here, the dispersion mean particle diameter of the fine particles (a) in the (?) Liquid was 27 nm as measured by a Microtrack particle size distribution meter manufactured by Nikkiso. (A): dispersant (B) = 1: 0.3: 2.2 in the weight ratio of heat ray shielding fine particles, dispersant (A) and dispersant (B) , And these were loaded in a stirring type vacuum dryer. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (γ)) of Comparative Example 3. As a result, 30 parts by weight of the dispersant (A) as the amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a). The content of methyl isobutyl ketone in the obtained composition (?) Was 3.2% by mass.

0.7% by mass of the obtained composition (?), 28.3% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, . The resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat-shrinkable laminated transparent heat-shrinkable film (hereinafter abbreviated as?) .

The resulting shielding film (gamma) was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Comparative Example 3 (hereinafter abbreviated as laminated transparent substrate y1) was obtained by a publicly known method. As shown in Table 1, the optical characteristics of the laminated transparent substrate 1 were 46.4% at a solar radiation transmittance of 77.0% and a haze value of 3.7% at a visible light transmittance of 77.0%.

On the other hand, the shielding film (gamma) was placed in a thermostatic bath at 120 DEG C for 5 days and then subjected to a heat resistance test for 5 days. The heat shielding laminated glass according to Comparative Example 3 Quot;). At this time, the yellow value b * between the laminated transparent base material (? 1) and the transparent base material (? 2) was measured, and the difference? B * was 5.48. The results are shown in Table 1.

The composition (?) Was stored at room temperature for 12 months. Then, 0.7% by mass of the stored composition (?), 28.3% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > The resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by a calender roll method to obtain a heat ray shielding film for a heat-shrinkable laminated transparent substrate (hereinafter, abbreviated as shielding film? .

The obtained shielding film (gamma ') was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Comparative Example 3 (hereinafter abbreviated as laminated transparent substrate (gamma 3)) was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent substrate 3 were 46.3% at a solar radiation transmittance of 76.9% and a haze value of 3.9% at a visible light transmittance of 76.9%. The results are shown in Table 1.

[Comparative Example 4]

(A), dispersant (A), and dispersant (having an acrylic main chain and an epoxy group as a functional group, having a molecular weight Mw of 9700, and a weight average molecular weight of 100,000) having an epoxy group as a functional group, a dispersing agent was added to the liquid (A) obtained in Example 1, (A): dispersant (A): dispersant (D) = 1: 1: 1, and these were mixed in a stirring type And loaded in a vacuum dryer. Then, the mixture was dried under reduced pressure at room temperature to remove methyl isobutyl ketone to obtain a heat-shrinkable fine particle-containing composition (hereinafter abbreviated as composition (隆)) of Comparative Example 4.

As a result, 100 parts by weight of the dispersant (A) as an amino group polymer dispersant was contained in 100 parts by weight of the fine particles (a).

The content of methyl isobutyl ketone in the obtained composition (?) Was 4.2% by mass.

0.6% by mass of the obtained composition (?), 28.4% by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition and then charged in a twin-screw extruder. Then, the resin composition was kneaded at 200 占 폚, extruded from a T-die, and calendered to a thickness of 0.7 mm to obtain a heat-shrinkable laminated transparent heat-shrinkable film for use in Comparative Example 4 (hereinafter abbreviated as shielding film?) .

The obtained shielding film (?) Was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass according to Comparative Example 4 (hereinafter abbreviated as laminated transparent substrate (delta 1)) was obtained by a publicly known method. As shown in Table 1, the optical properties of the laminated transparent substrate (? 1) had a solar radiation transmittance of 47.3% and a haze value of 0.9% at a visible light transmittance of 79.6%.

On the other hand, the shielding film (?) Was placed in a thermostatic bath at 120 占 폚 and subjected to a heat resistance test for 5 days. Then, the film was sandwiched between two sheets of inorganic glass and the heat ray shielding laminated glass (hereinafter referred to as laminated transparent substrate Quot;). At this time, the yellow lightness value b * of the laminated transparent base material (delta 1) together with the transparent base material (delta 2) was measured, and the difference? B * was 2.72. The results are shown in Table 1.

The composition (?) Was stored at room temperature for 12 months. Then, 0.6% by mass of the stored composition (?), 28.4% by mass of triethylene glycol di-2-ethylhexanonate as a plasticizer and 71% by mass of polyvinyl butyral resin were weighed and mixed to prepare a resin composition, Lt; / RTI > Then, the above resin composition was kneaded at 200 占 폚, extruded from a T-die, and 0.7 mm thick by a calender roll method to obtain a heat ray shielding transparent substrate heat shrinkable film (hereinafter abbreviated as shielding film? ') . The obtained shielding film (? ') Was sandwiched between two sheets of inorganic glass, and a heat ray shielding laminated glass of Comparative Example 4 (hereinafter abbreviated as laminated transparent substrate (? 3)) was obtained by a publicly known method.

As shown in Table 1, the optical characteristics of the laminated transparent substrate (? 3) were 62.3% at a solar radiation transmittance and 31.3% at a visible light transmittance of 77.5%. The results are shown in Table 1.

[Evaluation of Examples 1 to 12 and Comparative Examples 1 to 4]

In Examples 1 to 12, the heat-ray shielding fine particles were sufficiently contained with the amino group polymer dispersant having a high dispersing ability, so that the coagulation of the heat ray shielding fine particles could be prevented and the laminated transparent laminated transparent substrates A to K having low haze values could be obtained there was. In addition, since at least one kind of a hydroxyl-containing polymer dispersant or a carboxyl-based polymer dispersant having a high heat resistance is sufficiently contained, a laminated transparent substrate having a high heat resistance and suppressed yellowing in a heat resistance test can be obtained.

On the other hand, in Comparative Example 1, since the hydroxyl group-containing polymer dispersant having high heat resistance and the carboxyl group-containing polymer dispersant were not contained, yellowing occurred in the heat resistance test, and the appearance of the obtained laminated transparent substrate was damaged.

In Comparative Examples 2 and 3, the amino group polymer dispersant having a high dispersing ability with respect to the heat-ray shielding fine particles was contained or the content thereof was not sufficient, so that the composite tungsten oxide fine particles aggregated and the resulting laminated transparent substrate had a haze value of 2 %, And transparency was impaired.

In Comparative Example 4, since a dispersion agent having an epoxy group having a high heat resistance was contained in the same manner as in the hydroxyl group polymer dispersant and the carboxyl group polymer dispersant, a laminated transparent substrate having a high heat resistance and suppressed yellowing in the heat resistance test was obtained. However, since the epoxy group has reactivity with the amino group and lowers the dispersibility of the amino group polymer dispersant to the heat ray shielding fine particles, the transparent tungsten oxide fine particles Aggregation occurred, and the haze value of the obtained laminated transparent substrate exceeded 2%, impaired transparency.

Claims (8)

General formula M _y WO _Z (stage, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, Fe, Sn, Al, one or more kind elements selected from Cu, 0.1≤y≤0.5 , 2.2 ≤ z ≤ 3.0) and having a hexagonal crystal structure, and at least two dispersing agents, wherein the dispersant has an amino group as a functional group and has a thermal decomposition temperature At least one amino group polymer dispersant having a melting point of at least 200 DEG C,
Wherein the dispersant contains at least one kind of a hydroxyl group polymer dispersant and / or a carboxyl group polymer dispersant having an acrylic structure in the main chain and having a hydroxyl group (-OH group) and / or a carboxyl group (-COOH) as a functional group and having a thermal decomposition temperature of 200 ° C or higher and,
Wherein the content of the organic solvent having a boiling point of 120 占 폚 or less is 5 mass% or less. The method according to claim 1,
Wherein the amino group-containing polymer dispersant has an amine value of 5 to 100 mgKOH / g. The method according to claim 1 or 2,
Wherein the amino group polymer dispersant is contained in an amount of 50 parts by weight or more and 9900 parts by weight or less based on 100 parts by weight of the composite tungsten oxide fine particles. 4. The method according to any one of claims 1 to 3,
Wherein the organic solvent is at least one selected from the group consisting of toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, and ethanol. A heat-shrinkable film comprising the heat-ray shielding fine particle-containing composition according to any one of claims 1 to 4, and a polyvinyl acetal resin and a plasticizer kneaded to form a film. The heat ray shielding laminated transparent substrate according to claim 5, wherein the heat ray shielding film is present between two or more transparent substrates. General formula M _y WO _Z (stage, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, Fe, Sn, Al, one or more kind elements selected from Cu, 0.1≤y≤0.5 , 2.2? Z? 3.0) and having a hexagonal crystal structure, and a step of dispersing the dispersant in an organic solvent having a boiling point of 120 ° C or less to obtain a dispersion,
A second step of adding the dispersant or the dispersant dissolved in the organic solvent to the dispersion obtained in the first step and mixing them to obtain a mixture,
And a third step of drying the mixture until the content of the organic solvent contained in the mixture obtained in the second step is 5 mass% or less to obtain a composition containing heat ray shielding fine particles. Containing fine particle-containing composition according to claim 1. The method of claim 7,
Wherein the composite tungsten oxide fine particles in the dispersion are those having an average particle diameter of 40 nm or less.